Yitian Yang, Juntao Huang, Zirui Liu, Jiawei Fu, Xianjin Wu, Qiyuan Xiang, Wen Li, Kuncan Wang
ABSTRACT This review systematically summarizes recent advances in photothermal catalysis for converting CO 2 into high‐value C1 products (e.g., CO, CH 4 , and CH 3 OH). The review begins with the fundamental principles of photothermal synergy and explains how full‐spectrum utilization helps overcome thermodynamic and kinetic bottlenecks. This review focuses on rational catalyst design, particularly the role of alloyed catalysts in regulating electronic structures and surface reaction pathways. It also highlights how biomimetic photothermal catalysts mimic natural photosynthesis to achieve efficient energy‐to‐matter conversion. The review further surveys diverse catalytic systems, from Local Surface Plasmon Resonance (LSPR) metals and semiconductors to MOF/COF composites, and summarizes performance optimization strategies based on surface and defect engineering. Unlike previous reviews, a dedicated section discusses mass and heat transfer challenges in reactor engineering and scale‐up, extending the perspective from material microstructures to macroscopic system integration. Finally, the review synthesizes current challenges and identifies future directions in atomic‐level catalyst design, photo‐thermal coupling mechanisms, and process techno‐economic evaluation. This review aims to provide theoretical insights and a technical roadmap for designing efficient, stable, and scalable photothermal catalytic systems, ultimately advancing practical solar fuel production.